U.S. patent application number 10/668497 was filed with the patent office on 2004-03-25 for sheet for ink jet-recording.
This patent application is currently assigned to OJI PAPER CO., LTD.. Invention is credited to Morie, Masahiro, Nishio, Jun, Tsuchida, Tetsuo.
Application Number | 20040058099 10/668497 |
Document ID | / |
Family ID | 27531672 |
Filed Date | 2004-03-25 |
United States Patent
Application |
20040058099 |
Kind Code |
A1 |
Tsuchida, Tetsuo ; et
al. |
March 25, 2004 |
Sheet for ink jet-recording
Abstract
An ink jet-recording sheet for forming recorded images using
liquid ink comprises a combination of specific compounds, for
instance, 1,2-bis(2-hydroxyethylthio)ethane and a homopolymers or
copolymer of diallylamine type compounds such as
poly(diallylamine)hydrochloride, poly(diallylamine)sulfate,
poly(diallylamine)phosphate or poly(diallylamine)acetate. The ink
jet-recording sheet can ensure a high density of printed images,
can provide images having high quality, shows only a slight color
change and discoloration of printed images even when exposed to
ozone gas and is excellent in the long-term shelf life.
Inventors: |
Tsuchida, Tetsuo;
(Takarazuka, JP) ; Nishio, Jun; (Nishinomiya,
JP) ; Morie, Masahiro; (Amagasaki, JP) |
Correspondence
Address: |
CHRISTIE, PARKER & HALE, LLP
350 WEST COLORADO BOULEVARD
SUITE 500
PASADENA
CA
91105
US
|
Assignee: |
OJI PAPER CO., LTD.
|
Family ID: |
27531672 |
Appl. No.: |
10/668497 |
Filed: |
September 22, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10668497 |
Sep 22, 2003 |
|
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09971743 |
Oct 4, 2001 |
|
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6652930 |
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Current U.S.
Class: |
428/32.1 |
Current CPC
Class: |
B41M 5/5227 20130101;
B41M 5/5236 20130101; B41M 5/506 20130101; B41M 5/5245 20130101;
B41M 5/52 20130101 |
Class at
Publication: |
428/032.1 |
International
Class: |
B32B 003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 2000 |
JP |
2000-306042 |
Oct 27, 2000 |
JP |
2000-328193 |
Feb 19, 2001 |
JP |
2001-41444 |
Mar 30, 2001 |
JP |
2001-099029 |
May 8, 2001 |
JP |
2001-137180 |
Claims
What is claimed is:
1. A method of preparing an ink jet-recording sheet for forming
recorded images using liquid ink, which comprises the step of
applying an ink-receiving layer containing components (a) and (b)
onto a substrate. component (a): at least one member selected from
the group consisting of those represented by the following general
formulae (1) to (5) and salts of compounds represented by the
following general formulae (3) and (4); component (b): at least one
member selected from the group consisting of homopolymers of
diallylamine compounds represented by the following general formula
(6) and copolymers of the compounds of formula (6) with
copolymerizable ethylenically unsaturated compounds.
HO--(C.sub.2H.sub.4(S).sub.r).sub.p--R.sub.1 (1)
R.sub.2--(S).sub.t--(CH- .sub.2).sub.q--(S).sub.t--R.sub.3 (2)
HOOC--(CH.sub.2).sub.1--(S).sub.n --(CH.sub.2).sub.m--COOH (3)
2wherein R.sub.1, R.sub.2 and R.sub.3 each represents a C.sub.1 to
C.sub.4 alkyl group, a C.sub.1 to C.sub.4 hydroxyalkyl group or a
C.sub.1 to C.sub.4 dihydroxyalkyl group; R.sub.4 and R.sub.5 each
3represents a hydrogen atom or a C.sub.1 to C.sub.4 alkyl group;
R.sub.6 to R.sub.9 each represents a hydrogen atom, a C.sub.1 to
C.sub.4 alkyl group, a C.sub.1 to C.sub.4 alkylcarbonyl group or a
benzoyl group; R.sub.10 and R.sub.11 each represents a C.sub.1 to
C.sub.4 alkyl group or a C.sub.1 to C.sub.4 alkoxy group; R.sub.12
and R.sub.13 each represents a hydrogen atom or a methyl group;
R.sub.14 represents a hydrogen atom or a C.sub.1 to C.sub.4 alkyl
group; and HX represents an acid, and p represents an integer
ranging from 1 to 3; q represents an integer ranging from 1 to 6;
r, t, n and u each represents 1 or 2; 1 and m each represents an
integer ranging from 1 to 11; w represents an integer ranging from
1 to 6; y and z each represents 0 or an integer ranging from 1 to
3.
2. The method of claim 1, wherein the compound represented by the
general formula (1) is 1,2-bis(2-hydroxyethylthio)ethane.
3. The method of claim 1, wherein the compound represented by the
general formula (2) is 1,4-bis(2-hydroxyethylthio)butane.
4. The method of claim 1, wherein the compound represented by the
general formula (3) is 3,3'-thiodipropionic acid or
3,3'-dithiodipropionic acid.
5. The method of claim 1, wherein the compound represented by the
general formula (4) is 3,3'-dithiobis(2-aminopropionic acid).
6. The method of claim 1, wherein the compound represented by the
general formula (5) is 1,4-bis(phenylthio)butane or
1,6-bis(phenylthio)hexane.
7. The method of claim 1, which further comprises subjecting the
ink-receiving layer to a casting treatment.
8. The method of claim 1, which further comprises forming a glossy
layer on the ink-receiving layer.
9. A method of preparing an ink jet-recording sheet for forming
recorded images using liquid ink, which comprises the steps of
applying an ink-receiving layer containing the following component
(b) onto a substrate, and applying the following component (a) onto
the surface of the ink-receiving layer. component (a): at least one
member selected from the group consisting of those represented by
the following general formulae (1) to (5) and salts of compounds
represented by the following general formulae (3) and (4);
component (b): at least one member selected from the group
consisting of homopolymers of diallylamine compounds represented by
the following general formula (6) and copolymers of the compounds
of formula (6) with copolymerizable ethylenically unsaturated
compounds. HO--(C.sub.2H.sub.4(S).sub.r).sub.p--R.sub.1 (1)
R.sub.2--(S).sub.t--(CH.sub.2).sub.q--(S).sub.t--R.sub.3 (2)
HOOC--(CH.sub.2).sub.1--(S).sub.n--(CH.sub.2).sub.m--COOH (3)
4wherein R.sub.1, R.sub.2 and R.sub.3 each represents a C.sub.1 to
C.sub.4 alkyl group, a C.sub.1 to C.sub.4 hydroxyalkyl group or a
C.sub.1 to C.sub.4 dihydroxyalkyl group; 5R.sub.4 and R.sub.5 each
represents a hydrogen atom or a C.sub.1 to C.sub.4 alkyl group;
R.sub.6 to R.sub.9 each represents a hydrogen atom, a C.sub.1 to
C.sub.4 alkyl group, a C.sub.1 to C.sub.4 alkylcarbonyl group or a
benzoyl group; R.sub.10 and R.sub.11 each represents a C.sub.1 to
C.sub.4 alkyl group or a C.sub.1 to C.sub.4 alkoxy group; R.sub.12
and R.sub.13 each represents a hydrogen atom or a methyl group;
R.sub.14 represents a hydrogen atom or a C.sub.1 to C.sub.4 alkyl
group; and HX represents an acid, and p represents an integer
ranging from 1 to 3; q represents an integer ranging from 1 to 6;
r, t, n and u each represents 1 or 2; 1 and m each represents an
integer ranging from 1 to 11; w represents an integer ranging from
1 to 6; y and z each represents 0 or an integer ranging from 1 to
3.
10. The method of claim 9, wherein the compound represented by the
general formula (1) is 1,2-bis(2-hydroxyethylthio)ethane.
11. The method of claim 9, wherein the compound represented by the
general formula (2) is 1,4-bis(2-hydroxyethylthio)butane.
12. The method of claim 9, wherein the compound represented by the
general formula (3) is 3,3'-thiodipropionic acid or
3,3'-dithiodipropionic acid.
13. The method of claim 9, wherein the compound represented by the
general formula (4) is 3,3'-dithiobis(2-aminopropionic acid).
14. The method of claim 9, wherein the compound represented by the
general formula (5) is 1,4-bis(phenylthio)butane or
1,6-bis(phenylthio)hexane.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 09/971,743, filed Oct. 4, 2001, which claims priority of
Japanese Patent Application No. 2000-306042, filed Oct. 5, 2000;
Japanese Patent Application No. 2000-328193, filed Oct. 27, 2000;
Japanese Patent Application No. 2001-41444, filed Feb. 19, 2001;
Japanese Patent Application No. 2001-099029, filed Mar. 30, 2001;
and Japanese Patent Application No. 2001-137180, filed May 8, 2001,
the entirety of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a SHEET FOR INK
JET-RECORDING for use in forming recorded images using liquid ink
such as water-based ink and, in particular, to a sheet for ink
jet-recording (an INK JET-RECORDING SHEET), which never undergoes
any color change during or after long-term storage, which is a
disadvantage observed for the conventional ink jet-recording sheet,
while maintaining such advantages that it can ensure a high density
of full color-printed images formed thereon and that it is
excellent in ink absorptivity.
[0003] The ink jet-recording system, in which images are formed by
injecting water-based ink on a recording medium through a fine
nozzle, has widely been used in, for instance, printers for
terminal devices, facsimiles, plotters or devices for printing
account books and slips. This is because, for instance, it has a
low noise level during recording operations; it easily permits the
color printing; it also permits high-speed recording; and it is
less expensive as compared with other printing devices.
[0004] On the other hand, printers have rapidly been popularized
recently and they have increasingly been required to give finer and
more precise images at a high speed. In addition, there has
recently been developed a digital camera. Correspondingly,
recording mediums have been required to have higher recording
characteristic properties. More specifically, there has been
desired for the development of a recording medium, which is not
only excellent in ink absorptivity, recording density, water
resistance and storability, but also has image quality and shelf
life almost comparable to those observed for the images formed on
the silver halide system.
[0005] To satisfy such requirements, there have been proposed a
large number of sheets each comprising a substrate provided thereon
with an ink-receiving layer, which mainly comprises a pigment and a
binder. For instance, there have been reported a variety of methods
for applying, onto substrates, a coating layer comprising amorphous
silica and a polymer binder (Japanese Un-Examined Patent
Publication (hereunder referred to as "J.P. KOKAI" No. Sho
55-51583, J.P. KOKAI No. Sho 57-157786 and J.P. KOKAI No. Sho
62-158084); a coating layer comprising an ink-adsorbing pigment
such as zeolite (J.P. KOKAI No. Sho 56-144172); a coating layer
comprising finely pulverized silicic acid and a water-soluble resin
(J.P. KOKAI No. Sho 56-148583); and a coating layer comprising a
porous and cationic alumina hydrate (J.P. KOKAI No. Sho
60-232990).
[0006] Moreover, there have also been proposed methods, which
comprise incorporating, for instance, cationic polymers (J.P. KOKAI
No. Sho 56-84992, J.P. KOKAI No. Sho 60-49990 and J.P. KOKAI No.
Sho 61-125878); and basic latexes (J.P. KOKAI No. Sho 57-36692)
into the ink-receiving layers, in order to improve the water
resistance of printed letters.
[0007] Furthermore, there have also been proposed, for instance,
methods, which comprise adding, to the ink-receiving layer, at
least one member selected from the group consisting of metal oxides
and metal chlorides such as phosphorus tungstate, phosphorus
molybdate and chromic chloride, and tannic acid (J.P. KOKAI No. Sho
57-87987); an antioxidant such as a hindered phenol (J.P. KOKAI No.
Sho 57-74192); hindered amines (J.P. KOKAI No. Sho 61-146591); UV
light absorbers such as benzophenone type, benzotriazole type and
phenyl salicylic acid type ones (J.P. KOKAI No. Sho 57-74193, J.P.
KOKAI No. Sho 57-87988 and J.P. KOKAI No. Sho 63-222885); a
thiourea type compound (J.P. KOKAI No. Sho 61-163886); a specific
mercapto compound such as 2-mercaptobenzothiazole and
2-mercaptobenzimidazole (J.P. KOKAI No. Sho 61-177279); and a
dithiocarbamic acid salt, a thiuram salt, a thiocyanic acid ester
or a thiocyanic acid salt (J.P. KOKAI No. Hei 7-314882).
[0008] However, the full color ink jet recorded images formed
according to these techniques suffer from a problem of color change
during a long-term storage and in particular, when a phthalocyanine
dye is used as the dye for cyan color ink, these techniques have
still been insufficient since the images cause color change along
with the discoloration of the phthalocyanine dye.
SUMMARY OF THE INVENTION
[0009] Accordingly, it is an object of the present invention to
provide an ink jet-recording sheet, which does not suffer from the
drawbacks associated with the conventional ink jet-recording sheet,
and more specifically to an ink jet-recording sheet, which never
undergoes any color change during or after a long-term storage even
when the sheet is subjected to full color printing operations and
which permits the considerable reduction of such color change,
particularly observed when a phthalocyanine dye is used as the dye
for cyan color ink, along with the discoloration of the
phthalocyanine dye.
[0010] The inventors of this invention have conducted various
studies of an ink jet-recording sheet for forming recorded images
using liquid ink such as water-based ink, have found that when
incorporating, into the recording sheet, a specific compound
including a sulfur atom in the molecule and a polymer of a
diallylamine type compound, an ink jet-recording sheet free of any
drawback associated with the conventional ink jet-recording sheet
can be obtained and more specifically, the resulting ink
jet-recording sheet never undergoes any color change during or
after a long-term storage even when the sheet is subjected to full
color printing operations and the sheet permits the considerable
reduction of such color change, particularly observed when a
phthalocyanine dye is used as the dye for cyan color ink, along
with the discoloration of the phthalocyanine dye, and thus have
completed the present invention.
[0011] According to the present invention, there is thus provided
an ink jet-recording sheet for forming recorded images using liquid
ink, wherein the sheet comprises (a) at least one member selected
from the group consisting of those represented by the following
general formulae (1) to (5) and salts of compounds represented by
the following general formulae (3) and (4); and (b) at least one
member selected from the group consisting of homopolymers of
diallylamine compounds represented by the following general formula
(6) and copolymers of the compounds of formula (6) with
copolymerizable ethylenically unsaturated compounds.
HO--(C.sub.2H.sub.4(S).sub.r).sub.p--R.sub.1 (1)
R.sub.2--(S).sub.t--(CH.sub.2).sub.q--(S).sub.t--R.sub.3 (2)
HOOC--(CH.sub.2).sub.1--(S).sub.n--(CH.sub.2).sub.m--COOH (3) 1
[0012] wherein R.sub.1, R.sub.2 and R.sub.3 each represents a
C.sub.1 to C.sub.4 alkyl group, a C.sub.1 to C.sub.4 hydroxyalkyl
group or a C.sub.1 to C.sub.4 dihydroxyalkyl group; R.sub.4 and
R.sub.5 each represent a hydrogen atom or a C.sub.1 to C.sub.4
alkyl group; R.sub.6 to R.sub.9 each represents a hydrogen atom, a
C.sub.1 to C.sub.4 alkyl group, a C.sub.1 to C.sub.4 alkylcarbonyl
group or a benzoyl group; R.sub.10 and R.sub.11 each represents a
C.sub.1 to C.sub.4 alkyl group or a C.sub.1 to C.sub.4 alkoxy
group; R.sub.12 and R.sub.13 each represents a hydrogen atom or a
methyl group; R.sub.14 represents a hydrogen atom or a C.sub.1 to
C.sub.4 alkyl group; and HX represents an acid, and p represents an
integer ranging from 1 to 3; q represents an integer ranging from 1
to 6; r, t, n and u each represents 1 or 2; 1 and m each represents
an integer ranging from 1 to 11; w represents an integer ranging
from 1 to 6; y and z each represents 0 or an integer ranging from 1
to 3.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention will now be described in more detail
with reference to the following preferred embodiments. Specific
examples of the compounds represented by formulas (1) and (2)
include 2,2'-thiodiethanol, 2,2'-dithiodiethanol,
1,2-bis(2-hydroxyethylthio)etha- ne,
1,2-bis(2-hydroxyethyldithio)ethane,
2,2'-bis(2-hydroxyethylthio)dieth- yl sulfide,
2,2'-bis(2-hydroxyethylthio)diethyl disulfide,
bis(2-hydroxyethylthio)methane, bis(2-hydroxyethyldithio)methane,
1,3-bis(2-hydroxyethylthio)propane, 1,3-bis
(2-hydroxyethyl-dithio)propan- e,
1,4-bis(2-hydroxyethylthio)butane,
1,4-bis(2-hydroxyethyldithio)butane,
1,6-bis(2-hydroxyethylthio)hexane, 1,6-bis
(2-hydroxyethyldithio)hexane, ethylthioethanol, ethyldithioethanol,
n-propylthioethanol, isopropylthioethanol, isopropyldithioethanol,
n-butylthioethanol, 1-ethylthio-1-(2-hydroxyethylthio)methane,
1-ethylthio-2-(2-hydroxyethylt- hio)ethane,
1-ethylthio-3-(2-hydroxyethylthio)propane,
1-ethylthio-4-(2-hydroxyethylthio)butane,
1,1-bis(2,3-dihydroxypropylthio- )methane,
1,2-bis(2,3-dihydroxypropylthio)ethane, 1,3-bis(2,3-dihydroxypro-
pyldithio)propane, 1,4-bis(2,3-dihydroxypropylthio)butane,
1,6-bis(2,3-dihydroxypropylthio)hexane and
1-ethylthio-2-(2,3-dihydroxy-p- ropylthio)ethane.
[0014] Among these compounds, particularly preferably used herein
are 1,2-bis(2-hydroxyethylthio)ethane and
1,4-bis(2-hydroxyethylthio)butane because of their high color
change-inhibitory effect and high safety.
[0015] Specific examples of the compounds represented by formula
(3) are 2,2'-thiodiglycolic acid, 3,3'-thiodipropionic acid,
4,4'-thiodibutanoic acid, 6,6'-thiodicaproic acid,
8,8'-thiodicaprylic acid, 10,10'-thiodicapric acid, 12,
12'-thiodilauric acid, 2,2'-dithiodiglycolic acid,
3,3'-dithiodipropionic acid, 4,4'-dithiodibutanoic acid, 6,
6'-dithiodicaproic acid, 8,8'-dithiodicaprylic acid,
10,10'-dithiodicapric acid and 12,12'-dithiodilauric acid.
[0016] Among these compounds, particularly preferably used herein
are 3,3'-thiodipropionic acid and 3,3'-dithiodipropionic acid
because of their high color change-inhibitory effect and high
safety.
[0017] Specific examples of the compounds represented by the
general formula (4) are 3,3'-dithiobis(2-aminopropionic acid),
3,3'-thiobis(2-aminopropionic acid), dimethyl 3,
3'-dithiobis(2-aminoprop- ionate), dimethyl 3,3'-thiobis
(2-aminopropionate), diethyl 3,3'-dithiobis(2-aminopropionate),
diethyl 3,3'-thiobis(2-aminopropionate- ), diisopropyl
3,3'-dithiobis(2-aminopropionate), di n-butyl
3,3'-dithiobis(2-aminopropionate), 3,3'-dithiobis(2-N-acetyl
aminopropionic acid), 3,3'-thiobis(2-N-acetylaminopropionic acid),
dimethyl 3,3'-dithiobis(2-N-acetylaminopropionate), dimethyl
3,3'-thiobis(2-N-acetyl aminopropionate), dimethyl
3,3'-dithiobis(2-N-benzoyl aminopropionate) and dimethyl
3,3'-thiobis(2-N-benzoyl aminopropionate).
[0018] Particularly preferably used herein is 3,3'-dithiobis
(2-aminopropionic acid) among others, because of its high color
change-inhibitory effect and high safety.
[0019] Specific examples of the compounds represented by the
foregoing general formula (5) are 1,2-bis(phenylthio)ethane,
1,3-bis(phenylthio)propane, 1,4-bis (phenylthio)butane,
1,5-bis(phenylthio)pentane, 1,6-bis(phenylthio)hexane,
1,2-bis(4-methylphenylthio)ethane,
1,4-bis(4-methylphenylthio)butane, 1,6-bis
(4-methylphenylthio)hexane, 1-phenylthio-2-(4-methylphenylthio)et-
hane, 1-phenylthio-4-(4-methylphenylthio)butane,
1-phenylthio-6-(4-methylp- henylthio)hexane,
1,4-bis(2-methylphenylthio)butane,
1,4-bis(3-methylphenylthio)butane,
1,4-bis(3,4-dimethylphenylthio)butane,
1,4-bis(2,3,4-trimethylphenylthio)butane,
1,4-bis(4-ethylphenylthio)butan- e,
1,4-bis(4-t-butylphenylthio)butane, 1,
2-bis(4-methoxyphenylthio)ethane- ,
1,4-bis(4-methoxyphenylthio)butane,
1,6-bis(4-methoxyphenylthio)hexane,
1,4-bis(4-isopropoxyphenylthio)butane,
1-phenylthio-4-(4-methoxyphenylthi- o)butane and
1-phenylthio-4-(4-isopropoxyphenylthio)butane.
[0020] In this respect, particularly preferably used herein are
1,4-bis(phenylthio)butane and 1,6-bis(phenylthio)hexane among
others, because of their high color change-inhibitory effect.
[0021] Examples of ions as the counterparts of the salts of the
compounds represented by the general formula (3) or (4) include
sodium, potassium, magnesium, calcium, ammonium and zinc.
[0022] The acid represented by the foregoing general formula HX of
(6) may be either inorganic or organic ones and specific examples
thereof include inorganic acids such as hydrochloric acid, sulfuric
acid, nitric acid, phosphoric acid, pyrophosphoric acid and
metaphosphoric acid; and organic acids such as formic acid, acetic
acid, propionic acid, methanesulfonic acid and p-toluenesulfonic
acid. Among these acids, particularly preferably used herein are
hydrochloric acid and sulfuric acid, because of their high color
change-inhibitory effect. In the foregoing formulas, R.sub.12,
R.sub.13 and R.sub.14 preferably represent a hydrogen atom.
[0023] Examples of the homopolymers and copolymers of the
diallylamine compounds represented by the general formula (6) are
poly(diallylamine)hydrochloride, poly(diallylamine)sulfate,
poly(diallylamine)phosphate, poly(diallylamine)acetate,
poly(diallylamine)propionate, poly(diallylamine)methanesulfonate,
poly(diallylmethylamine)hydrochloride,
poly(diallylmethylamine)sulfate,
poly(diallylethylamine)hydrochloride,
poly(diallylethylamine)sulfate,
poly(diallyl-n-propylamine)hydrochloride,
poly(diallyl-n-butylamine)hydro- chloride,
poly(di-2-methylallylamine)hydrochloride,
poly(di-2-methylallylamine)sulfate, diallylamine
hydrochloride-acrylamide copolymer, diallylamine sulfate-acrylamide
copolymer, diallylamine phosphate-acrylamide copolymer,
diallylmethylamine hydrochloride-acrylamide copolymer,
diallylmethylamine sulfate-acrylamide copolymer, diallylmethylamine
phosphate-acrylamide copolymer, diallylethylamine
hydrochloride-acrylamide copolymer, diallylamine
hydrochloride-sulfur dioxide copolymer, diallylamine sulfate-sulfur
dioxide copolymer, diallylmethylamine hydrochloride-sulfur dioxide
copolymer and diallylethylamine hydrochloride-sulfur dioxide
copolymer. Among these polymers and copolymers, preferably used
herein are those having a molecular weight ranging from 10,000 to
200,000.
[0024] These polymers and copolymers ensure the achievement of the
synergistic effects of improving water resistance and color
change-inhibition.
[0025] As has been discussed above, full color ink jet-recorded
images undergo color change during a long-term storage and, in
particular, when a phthalocyanine dye is used as the dye for cyan
color ink, a significant color change is observed along with the
discoloration of the dye. It would be recognized that this color
change is caused due to the easy and preferential oxidation of the
cyan dye carrying a phthalocyanine skeleton by gases present in the
air, in particular, those having a strong oxidative effect such as
ozone.
[0026] Although the reason why the compounds represented by the
general formulas (1) to (5) and salts of the compounds of formulas
(3) and (4) are particularly effective in the inhibition of any
color change of the ink jet-recording sheet has not yet been
clearly elucidated, it would be recognized that the compounds of
formulas (1) to (5) and the salts of the compounds of formulas (3)
and (4) are quite susceptible to a gas having a strong oxidative
effect such as ozone, that they are accordingly oxidized prior to
the oxidation of the cyan dye and therefore, the cyan dye is
protected from any oxidation.
[0027] Moreover, the compounds formed through the oxidation of the
compounds of formulas (1) to (5) and salts of formulas (3) and (4)
are colorless and therefore, it is important characteristic
properties of the ink jet-recording sheet of the present invention
that it does not suffer from a problem of, for instance, any
yellowing of the sheet thereof.
[0028] The content of the compounds represented by the foregoing
formulas (1) to (5) and salts of formulas (3) and (4) in the ink
jet-recording sheet is on the order of about 0.1 to 4 g/m.sup.2 and
preferably 0.2 to 2 g/m.sup.2. This is because if the content
thereof is less than 0.1 g/m.sup.2, the intended effect of
improving the shelf life of the recorded images may be
insufficient, while if it exceeds 4 g/m.sup.2, the quality of the
resulting images may be impaired.
[0029] The content of the homopolymers and copolymer of the
compound represented by formula (6) in the ink jet-recording sheet
in general ranges from 1 to 100 parts by weight and preferably 5 to
50 parts by weight per 100 parts by weight of the pigment. This is
because if the content thereof is less than the lower limit, the
resulting sheet may be insufficient in the effect of improving the
shelf life and it is difficult to obtain the desired effects of
improving, for instance, the water resistance and density of
printed letters. On the other hand, if the content exceeds the
upper limit, the density of printed letters may be reduced and
images may cause bleeding.
[0030] As methods for preparing an ink jet-recording sheet
comprising the compound represented by the foregoing formulas (1)
to (5) and salts of formulas (3) and (4) and the homopolymers or
copolymer of the compound of the general formula (6), there may be
listed, for instance, a method in which base paper is coated or
impregnated with a coating liquid containing specific compounds
using a size press, for instance, during paper-making process; a
method which comprises the steps of applying a coating liquid for
forming an ink-receiving layer prepared by mixing an ink absorptive
pigment, an adhesive and specific compounds onto a substrate such
as paper (acidic paper, neutral paper), synthetic paper, a plastic
film or a non-woven fabric using a coating machine and then drying
the coated layer to give an ink-receiving layer; and a method which
comprises the step of applying a coating liquid containing specific
compounds onto the surface of an ink-receiving layer comprising a
pigment, an adhesive and a specific polymer.
[0031] Among these methods, preferably used herein is the method in
which the foregoing specific compounds are incorporated into the
ink-receiving layer since the method is highly effective in
inhibiting any color change of images.
[0032] If the compounds of the foregoing formulas (1) to (5) and
the salts of the compounds of formulas (3) and (4) are soluble in
water, an aqueous solution thereof is incorporated into a coating
liquid for forming an ink-receiving layer or applied onto an
ink-receiving layer. On the other hand, if they are less soluble in
water, they are finely pulverized in an agitation-pulverization
machine such as a ball mill, an attritor, a sand mill or a colloid
mill, while using water as a dispersion medium.
[0033] Examples of substrates for ink jet-recording sheets usable
herein are paper (acidic paper, neutral paper), synthetic paper, a
plastic film, a non-woven fabric, a plastic film laminated with
coated paper or wood-free paper through an adhesive layer or a
laminate of paper with a plastic film. Examples of such plastic
films are polyester, polypropylene and nylon films.
[0034] Examples of pigments to be incorporated into the
ink-receiving layer are zeolite, precipitated calcium carbonate,
ground calcium carbonate, magnesium carbonate, kaolin, talc,
calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc
sulfide, zinc carbonate, satin white, aluminum silicate,
diatomaceous earth, calcium silicate, magnesium silicate, amorphous
silica, aluminum hydroxide, alumina, alumina hydrate,
aluminosilicate, lithopone and urea-formalin resin filler. These
pigments may be used alone or in any combination of at least two of
them.
[0035] Preferably used herein are amorphous silica, alumina and
alumina hydrate among others, because of their excellent
ink-absorbing capacity.
[0036] The amount of these pigments to be incorporated into the
ink-receiving layer ranges from about 20 to 90% by weight and
preferably 30 to 80% by weight on the basis of the total weight of
the solid contents of the ink-receiving layer. In this respect, if
the amount of the pigment exceeds 90% by weight, the resulting
ink-receiving layer may have reduced film strength, while if the
amount thereof is less than 20% by weight, the resulting
ink-receiving layer may have a reduced ink-absorbing capacity and
insufficient ink-drying properties after recording and the quality
of images may correspondingly be impaired.
[0037] Moreover, in the present invention, it is also possible to
simultaneously use a polymer, which shows cationic characteristics
through dissociation when dissolved or emulsified in water, as a
cationic polymer component. Examples of such cationic polymers are
poly(diallyldimethylammonium chloride), diallyldimethylammonium
chloride-acrylamide copolymer, diallyldimethylammonium
chloride-sulfur dioxide copolymer, poly(allylamine)hydrochloride,
allylamine hydrochloride-diallylamine hydrochloride copolymer,
N-vinyl acrylamidine hydrochloride-acrylamide copolymer,
dialkylamine-epichlorohydrin addition polymer, polyamide polyamine
epichlorohydrin polymerized product, dicyandiamide-formalin
polycondensate, polyethylene polyamine-dicyandiamide
polycondensate, poly(ethyleneimine)hydrochloride,
poly(meth)acryloyloxyalkyl dialkylamine hydrochloride,
(meth)acryloyloxyalkyl dialkylamine hydrochloride-acrylamide
copolymer, poly(meth)acryloyloxyalkyl trialkylammonium chloride,
(meth)acryloyloxyalkyl trialkylammonium chloride-acrylamide
copolymer, poly(meth)acrylamide alkyldialkylamine hydrochloride,
(meth)acrylamide alkyldialkylamine hydrochloride-acrylamide
copolymer, poly(meth)acrylamide alkyl trialkylammonium chloride and
(meth)acrylamide alkyl trialkylammonium chloride-acrylamide
copolymer.
[0038] The ink-receiving layer further comprises, as an adhesive,
for instance, aqueous adhesives such as starch derivatives such as
oxidized starch and etherified starch; cellulose derivatives such
as carboxymethyl cellulose and hydroxyethyl cellulose; casein,
gelatin, soybean protein, completely (or partially) saponified
polyvinyl alcohol, silanol-modified polyvinyl alcohol, acetoacetyl
group-modified polyvinyl alcohol, salts of styrene-maleic anhydride
copolymer, styrene-butadiene type latexes, acryl type latexes,
polyester polyurethane type latexes and vinyl acetate type latexes;
or organic solvent-soluble resins such as poly (methyl
methacrylate), polyurethane resins, unsaturated polyester resins,
vinyl chloride-vinyl acetate copolymer, polyvinyl butyral and alkyd
resins. These adhesives may be used alone or in any
combination.
[0039] These adhesives are in general used in an amount ranging
from about 1 to 200 parts by weight and preferably about 10 to 100
parts by weight per 100 parts by weight of the pigment.
[0040] Further, the ink-receiving layer may additionally comprise
other additives such as a pigment dispersant, a thickening agent, a
cross-linking agent, a fluidity-improving agent, an anti-foaming
agent, a foam-inhibitor, a releasing agent, a foaming agent, a
penetrating agent, a coloring dye, a coloring pigment, a
fluorescent brightener, an antiseptic agent, an anti-fungus agent
and/or a water resistance-imparting agent, in an appropriate
amount.
[0041] The ink-receiving layer can be prepared by applying a
coating liquid for forming ink-receiving layers onto at least one
side of a substrate using a coating means such as a bar coater, a
blade coater, an air-knife coater, a gravure coater, a die coater
or a curtain coater, in a coated amount, as determined after
drying, ranging from about 2 to 30 g/m.sup.2 and then drying the
coated layer. This is because if the coated amount is less than 2
g/m.sup.2, the quality of the resulting image may be impaired,
while if it exceeds 30 g/m.sup.2, the resulting sheet may have
reduced film strength.
[0042] After the formation of the ink-receiving layer, the ink
jet-recording sheet may be passed through a roll nip under pressure
using, for instance, a super calendar or a gloss-calendar to thus
impart surface smoothness to the layer in order to, for instance,
make the layer highly glossy.
[0043] A glossy layer may further be applied onto the foregoing
ink-receiving layer. This glossy layer may principally comprise a
resin. Moreover, the glossy layer may likewise comprise a pigment
in addition to the resin. The glossy layer is preferably porous or
permeable to liquids insofar as the glossiness is never impaired so
that ink may rapidly pass through the layer or may be absorbed by
the same. To this end, it is desirable to incorporate a pigment
into the layer or to select such drying conditions that the resin
is not completely converted into a film and that the glossiness is
not impaired.
[0044] Pigments used in the glossy layer may be the same as those
listed above in connection with the ink-receiving layer, but
preferred are, for instance, colloidal silica, amorphous silica,
aluminum oxide, aluminosilicate, zeolite and synthetic smectite,
because of their excellent glossiness, transparency and
ink-absorbing ability. These pigments are desirably included in the
glossy layer in an amount ranging from 10 to 80% by weight. The
higher the specific surface area of a pigment as determined
according to the BET formula, the higher the ink-absorbing ability
thereof and therefore, the specific area thereof is preferably not
less than 150 m.sup.2/g. The average particle size of the pigment
preferably ranges from 0.01 to 5 .mu.m and more preferably 0.05 to
1 .mu.m. If using, as a pigment, fine silica particles whose
average particle size of the primary particles is not less than 3
nm and not more than 40 nm and whose average particle size of the
secondary particles is not less than 10 nm and not more than 500
nm, the resulting product is particularly excellent in the
glossiness and printed density. If the glossy layer comprises a
pigment as a main component (10 to 80 wt %), the resulting product
is particularly excellent in the ink-absorbing ability.
[0045] In this case, the glossy layer is excellent in both the
ink-absorbing ability and transparency. Therefore, if a cationic
compound is incorporated into the glossy layer, a dye for ink is
effectively fixed to the glossy layer and the product is liable to
be quite excellent in the printed density because of the
synergistic effect with the transparency of the glossy layer.
[0046] Examples of resins used for forming the glossy layer are
water-soluble resins (for instance, polyvinyl alcohols such as
polyvinyl alcohol, cation-modified polyvinyl alcohol and
silanol-modified polyvinyl alcohol; casein, soybean proteins,
synthetic proteins, starches; and cellulose derivatives such as
carboxymethyl cellulose and methyl cellulose); water-dispersible
resins, for instance, conjugated diene polymer type latexes such as
styrene-butadiene copolymer, styrene-acrylates and copolymer methyl
methacrylate-butadiene copolymer latexes, vinyl copolymer type
latexes such as styrene-vinyl acetate copolymer latexes; aqueous
acrylic resins, aqueous polyurethane resins and aqueous polyester
resins as well as a variety of resins (adhesives) known and
currently used in the field of the coated paper. These resins for
forming the glossy layer may be used alone or in any combination of
at least two of them.
[0047] In this connection, if the glossy layer is mainly formed
from a resin, it is particularly preferred to use, as a main
component, a polymer or copolymer (hereunder collectively referred
to as "polymer") obtained by polymerizing monomers having
ethylenically unsaturated bonds (hereunder referred to as
"ethylenic monomer"). It is also possible to use substituted
derivatives of these polymers. Moreover, usable herein also include
composites prepared by polymerizing the foregoing ethylenic
monomers in the presence of colloidal silica to thus form Si--O--R
(wherein R represents a polymer moiety) bonds between these
components or those obtained by introducing, in advance, functional
groups reactive with colloidal silica such as SiOH groups into the
foregoing polymers and then reacting the product with colloidal
silica. If such a composite is used, the resulting product is
liable to be excellent in the glossiness and ink-absorbing
ability.
[0048] Moreover, in another embodiment, if using a casting method,
the resulting product may be excellent in the ability of releasing
from the casting drum. The particle size of the composite particles
is not restricted to any particular range, but the particle size,
for instance, ranges from about 20 to 200 nm.
[0049] In an embodiment in which the glossy layer is formed by a
casting method using a heated mirror-finishing drum, the foregoing
polymer preferably has a glass transition temperature of not less
than 40.degree. C. and more preferably 50 to 100.degree. C. If the
polymer has a lower glass transition temperature, the film-forming
rate during drying is extremely high and the surface porosity of
the resulting film is reduced. This may in turn lead to the
reduction of the ink-absorbing speed of the glossy layer. In
addition, the drying temperature is an important factor. This is
because if the drying temperature is too high, the film formation
excessively proceeds during the drying step, the surface porosity
of the resulting product is lowered and as a result, the
ink-absorbing speed is reduced. On the other hand, if the drying
temperature is too low, the resulting product has a tendency of
reducing its glossiness and the productivity rate thereof is also
reduced.
[0050] A composition for forming a glossy layer may appropriately
comprise a variety of auxiliary agents generally used in the field
of the coated paper for printing and ink jet-recording paper for
the control of the whiteness, viscosity and flowability and
examples thereof are pigments, anti-foaming agents, coloring
agents, antistatic agents, antiseptics, dispersants, thickening
agents and releasing agents. In addition, a cationic compound such
as the foregoing cationic resins may be incorporated into the
glossy layer to thus impart an ability of fixing dyes for ink even
to the glossy layer. The coated amount of the glossy layer ranges
from 0.2 to 30 g/m.sup.2 and preferably 1 to 20 g/m.sup.2, as
expressed in terms of the amount of the solid contents.
[0051] In addition, an ink jet-recording sheet having higher
surface glossiness may be obtained by, for instance, applying a
gloss-developing layer and subjecting the layer to a casting
treatment or directly subjecting the ink-receiving layer to a
casting treatment. Such a casting treatment can be carried out by,
for instance, a wet method, a gelation method and a re-wet method.
The wet method comprises the steps of pressing a gloss-developing
layer, which layer can be an ink jet-recording layer, applied onto
a base paper against a heated mirror-finished drum surface while
the gloss-developing layer is still in the wet condition to thus
obtain highly glossy finishing. The gelation method comprises the
steps of bringing a gloss-developing layer, which layer can be an
ink jet-recording layer, applied onto base paper into contact with
a gelling agent-containing bath while the gloss-developing layer is
still in the wet condition and then pressing the gloss-developing
layer in the gelatinized condition against a heated drum surface to
thus obtain highly glossy finishing. The re-wet method comprises
the steps of once drying a gloss-developing layer, which layer can
be an ink jet-recording layer, in the wet condition, again bringing
the layer into contact with a wetting liquid and then pressing the
layer against a heated drum surface to thus obtain highly glossy
finishing.
[0052] It is a matter of course that a protective layer may be
applied onto the back face of the substrate and/or an intermediate
layer may be formed between the substrate and the ink-receiving
layer. More specifically, a variety of techniques known in the
field of the ink jet-recording sheet production may be used in the
present invention.
[0053] The term "liquid ink" used for recording or printing images
is a recording liquid comprising a coloring agent, a liquid medium
and other additives. In this connection, the liquid ink includes
water based ink, and oil based ink.
[0054] Examples of coloring agents for water based ink are various
kinds of water-soluble dyes such as direct dyes, acid dyes and
reactive dyes.
[0055] In addition, examples of such liquid mediums for water-based
ink include water or combinations of water and water-soluble
organic solvents.
[0056] Specific examples of water-soluble organic solvents are
monohydric alcohols such as ethyl alcohol and isopropyl alcohol;
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol and glycerin; and lower alkyl ethers of
polyhydric alcohols such as triethylene glycol monomethyl ether,
and triethylene glycol monoethyl ether.
[0057] The ink of the present invention may additionally comprise
other additives such as a pH adjuster, a sequestering agent, an
anti-fungus agent, a viscosity modifier, a surface tension
modifier, a surfactant and a rust-proofing agent.
[0058] The present invention will hereunder be described in more
detail with reference to the following working Examples, but the
present invention is not restricted to these specific examples at
all. In the following examples, the terms "part" and "%" represent
"part by weight" and "% by weight" respectively, unless otherwise
specified.
EXAMPLE I-1
[0059] Preparation of Coating Liquid a for Forming Ink-Receiving
Layer
[0060] A coating liquid A for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fine Seal X60 available from Tokuyama Co.,
Ltd.), 250 parts of a 10% aqueous solution of silanol-modified
polyvinyl alcohol (trade name: R1130 available from Kuraray Co.,
Ltd.), 75 parts of a 40% aqueous solution of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.), 200 parts of a 5%
aqueous solution of 1,2-bis(2-hydroxyethylthio)ethane and small
amounts of an anti-foaming agent and a dispersant as well as water,
and the coating liquid had a solid content of 15%.
[0061] Preparation of Ink Jet-Recording Sheet
[0062] The coating liquid A prepared above was applied onto
wood-free paper having a basis weight of 65 g/m.sup.2 an amount of
12 g/m.sup.2 as expressed in terms of the solid content using a
wire bar and then dried to form an ink-receiving layer.
Subsequently, the layer was subjected to a treatment with a super
calender to thus form an ink jet-recording sheet.
EXAMPLES I-2 TO I-10
[0063] The same procedures used in Example I-1 were repeated except
that the following compounds were substituted for the
1,2-bis(2-hydroxyethylth- io)ethane used in Example I-1 to thus
form each corresponding ink jet-recording sheet.
EXAMPLE I-2
[0064] 1,4-bis(2-hydroxyethylthio)butane
EXAMPLE I-3
[0065] 2,2'-thiodiethanol
EXAMPLE I-4
[0066] 2,2'-dithiodiethanol
EXAMPLE I-5
[0067] bis(2-hydroxyethylthio)methane
EXAMPLE I-6
[0068] 1,6-bis(2-hydroxyethylthio)hexane
EXAMPLE I-7
[0069] ethylthioethanol
EXAMPLE I-8
[0070] isopropylthioethanol
EXAMPLE I-9
[0071] 1-ethylthio-2-(2-hydroxyethylthio)ethane
EXAMPLE I-10
[0072] 1,2-bis(2,3-dihydroxypropylthio)ethane
EXAMPLES I-11 AND I-12
[0073] The same procedures used in Example I-1 were repeated except
that the following compounds were substituted for the diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.) used in Example I-1 to
form each corresponding ink jet-recording sheet.
EXAMPLE I-11
[0074] diallylamine hydrochloride-sulfur dioxide copolymer (trade
name: PAS-92 available from Nitto Boseki Co., Ltd.)
EXAMPLE I-12
[0075] poly(diallylmethylamine)hydrochloride (PAS-M-1 available
from Nitto Boseki Co., Ltd.)
EXAMPLE I-13
[0076] Preparation of Coating Liquid B for Forming Ink-Receiving
Layer
[0077] A coating liquid B for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fine Seal X60 available from Tokuyama Co.,
Ltd.), 250 parts of a 10% aqueous solution of silanol-modified
polyvinyl alcohol (trade name: R1130 available from Kuraray Co.,
Ltd.), 75 parts of a 40% aqueous solution of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.) and small amounts of an
anti-foaming agent and a dispersant as well as water, and which had
a solid content of 15%.
[0078] Preparation of Ink Jet-Recording Sheet
[0079] The coating liquid B prepared above was applied onto
wood-free paper having a basis weight of 65 g/m in an amount of 12
g/m.sup.2 as expressed in terms of the solid content using a wire
bar and then dried to form an ink-receiving layer. Subsequently, a
5% aqueous solution of 1,2-bis(2-hydroxyethylthio)ethane was
applied onto the layer in an amount of 1.0 g/m as expressed in
terms of the solid content using a wire bar and then dried.
Thereafter, the layer thus treated was subjected to a treatment
with a super calender to thus form an ink jet-recording sheet.
EXAMPLE I-14
[0080] Preparation of Coating Liquid C for Forming Gloss-Developing
Layer
[0081] A coating liquid C for forming a gloss-developing layer was
prepared, which included 100 parts of a composite of
styrene-2-ethylhexyl acrylate copolymer having a glass transition
temperature of 75.degree. C. and colloidal silica (the weight ratio
of the copolymer to the colloidal silica was found to be 40:60), 5
parts of a copolymer of an alkyl vinyl ether and a maleic acid
derivative as a thickening-dispersant and 3 parts of lecithin as a
releasing agent and which had a solid content of 30%.
[0082] Preparation of Ink Jet-Recording Sheet
[0083] An ink-receiving layer was formed on the surface of
wood-free paper having a basis weight of 65 g/m.sup.2 by applying
the coating liquid A prepared in Example I-1 in an amount of 12
g/m.sup.2 as expressed in terms of the solid content using a wire
bar and then dried. Immediately after the coating liquid C prepared
above was applied onto the ink-receiving layer, the layer was
pressed against a mirror-finished drum whose surface temperature
was set at 85.degree. C., followed by drying and releasing the
layer from the drum surface to thus give a glossy type ink
jet-recording sheet provided thereon with a glossy layer. In this
respect, the coated amount of the glossy layer was found to be 8
g/m.sup.2 as expressed in terms of the solid content.
EXAMPLE I-15
[0084] Preparation of Coating Liquid D for Forming Gloss-Developing
Layer
[0085] A coating liquid D for forming a gloss-developing layer was
prepared, which included 100 parts of a composite of
styrene-2-ethylhexyl acrylate copolymer having a glass transition
temperature of 75.degree. C. and colloidal silica (the weight ratio
of the copolymer to the colloidal silica was found to be 40:60), 10
parts of 1,2-bis(2-hydroxyethylthio)eth- ane, 5 parts of a
copolymer of an alkyl vinyl ether and a maleic acid derivative as a
thickening-dispersant and 3 parts of lecithin as a releasing agent
and which coating liquid D had a solid content of 30%.
[0086] Preparation of Ink Jet-Recording Sheet
[0087] An ink-receiving layer was formed on the surface of
wood-free paper having a basis weight of 65 g/m.sup.2 by applying
the coating liquid A prepared in Example I-1 in an amount of 12
g/m.sup.2 as expressed in terms of the solid content using a wire
bar and then dried. Immediately after the coating liquid D prepared
above was applied onto the ink-receiving layer, the layer was
pressed against a mirror-finished drum whose surface temperature
was set at 85.degree. C. to dry, and the layer was released from
the drum surface to thus give a glossy type ink jet-recording sheet
provided thereon with a glossy layer. In this respect, the coated
amount of the glossy layer was found to be 8 g/m.sup.2 as expressed
in terms of the solid content.
COMPARATIVE EXAMPLE I-1
[0088] The same procedures used in Example I-1 were repeated except
that 1,2-bis(2-hydroxyethylthio)ethane was not used at all to thus
give an ink jet-recording sheet.
COMPARATIVE EXAMPLE I-2
[0089] The same procedures used in Example I-1 were repeated except
for using 50 parts of a 20% dispersion of dilauryl
3,3'-thiodipropionate prepared by the following method in place of
200 parts of the 5% aqueous solution of
1,2-bis(2-hydroxyethylthio)ethane used in Example I-1 to give an
ink jet-recording sheet.
[0090] Preparation of Dispersion Containing Dilauryl
3,3'-Thiodipropionate
[0091] A dispersion was prepared by pulverizing a composition
containing 100 parts of dilauryl 3,3'-thiodipropionate, 5 parts of
sulfonate group-modified polyvinyl alcohol (trade name: Goselane
L-3266 available from The Nippon Synthetic Chemical Industry, Co.,
Ltd.) and small amounts of a surfactant and an anti-foaming agent
as well as water, and having a solid content of 20% in a sand
grinder till the average particle size was reduced to 0.5
.mu.m.
COMPARATIVE EXAMPLE I-3
[0092] The same procedures used in Comparative Example I-2 were
repeated except that 2,6-di-tert-butyl-p-cresol was used instead of
the dilauryl 3,3'-thiodipropionate used in Comparative Example I-2
to give an ink jet-recording sheet.
COMPARATIVE EXAMPLE I-4
[0093] The same procedures used in Example I-1 were repeated except
that poly(diallyldimethylammonium)chloride (trade name: Unisense
CP-103 available from Senka Co., Ltd.) was used instead of the
diallylamine hydrochloride-acrylamide copolymer (trade name:
Sumirez Resin 1001 available from Sumitomo Chemical Co., Ltd.) used
in Example I-1 to give an ink jet-recording sheet.
COMPARATIVE EXAMPLE I-5
[0094] The same procedures used in Example I-1 were repeated except
that polyethylene polyamine-dicyandiamide polycondensate (trade
name: Neofix RP-70 available from Nikka Chemical Co., Ltd.) was
used instead of the diallylamine hydrochloride-acrylamide copolymer
(trade name: Sumirez Resin 1001 available from Sumitomo Chemical
Co., Ltd.) used in Example I-1 to give an ink jet-recording
sheet.
COMPARATIVE EXAMPLE I-6
[0095] The same procedures used in Example I-14 were repeated
except that 1,2-bis(2-hydroxyethylthio)ethane was not used at all
to give an ink jet-recording sheet.
[0096] The ink jet recording sheets prepared in the foregoing
Examples and Comparative Examples were used in solid printing with
mixed black ink obtained by the color mixing of cyan, magenta and
yellow dyes and with cyan ink and also used in printing ISO-400
images ("Highly Precise and Fine Color Digital Standard Image Data:
ISO/JIS-SCID", p. 13, Kind of Image: Portrait, published by
Foundation: Nippon Kikaku Kyokai) using Epson Ink Jet Printer
PM-800C and then these sheets were evaluated according to the
following methods. The results thus obtained are listed in the
following Table 1. In this connection, a phthalocyanine dye is used
in PM-800C as a cyan dye.
[0097] Density of Printed Matter
[0098] The densities of the solid portion printed with the mixed
black ink obtained by the color mixing of cyan, magenta and yellow
dyes and with cyan ink were determined using Macbeth's Densitometer
(Model RD-914 available from Macbeth Company).
[0099] Quality of Image
[0100] The ISO-400 images were observed with the naked eyes to thus
evaluate the quality thereof.
[0101] Evaluation Criteria
[0102] .circleincircle.: quite excellent;
[0103] .smallcircle.: excellent; and
[0104] x: inferior.
[0105] Resistance to Ozone
[0106] These sheets were inspected for the resistance to ozone,
which was recognized to have strong correlation with the long-term
storability. Solid printed portions and ISO-400 images were formed
on these sheets with the mixed black ink obtained by the color
mixing of cyan, magenta and yellow dyes and with cyan ink and then
allowed to stand in a container having an ozone concentration of 10
ppm over 12 hours. In case of the solid printed portion, the
Macbeth's density was determined after the foregoing test to thus
calculate the rate of remaining image according to the following
equation. On the other hand, the ISO-400 image was visually
inspected for the degree of color change, which was ranked
according to the following evaluation criteria: Rate of Remaining
Image (%)=[(Density Observed After Treatment)/(Density Observed
Prior to Treatment)].times.100
[0107] Evaluation Criteria
[0108] .circleincircle.: There was not observed any color change
and discoloration.
[0109] .smallcircle.: There was observed a slight color change and
discoloration, but the image could practically be acceptable.
[0110] x: There was observed severe color change and discoloration
and the image could not practically be acceptable.
1 TABLE 1 Resistance to Ozone Rate of Rate of Printed Quality
Remaining Remaining Ex. Density of Black Image Cyan Image No. Black
Cyan Image (%) (%) Image I-1 1.77 1.56 .circleincircle. 85.3 88.5
.circleincircle. I-2 1.74 1.53 .circleincircle. 84.5 87.5
.circleincircle. I-3 1.72 1.50 .largecircle. 76.5 77.4
.largecircle. I-4 1.70 1.48 .largecircle. 77.6 79.5 .largecircle.
I-5 1.73 1.51 .largecircle. 76.8 78.8 .largecircle. I-6 1.73 1.50
.largecircle. 76.8 79.7 .largecircle. I-7 1.71 1.52 .largecircle.
76.8 77.7 .largecircle. I-8 1.70 1.51 .largecircle. 76.1 77.2
.largecircle. I-9 1.73 1.52 .largecircle. 78.5 79.2 .largecircle.
I-10 1.71 1.52 .largecircle. 77.8 78.9 .largecircle. I-11 1.73 1.51
.circleincircle. 84.2 87.3 .circleincircle. I-12 1.72 1.50
.circleincircle. 80.5 82.7 .circleincircle. I-13 1.75 1.53
.largecircle. 85.5 88.9 .circleincircle. I-14 1.85 1.64
.circleincircle. 84.7 87.4 .circleincircle. I-15 1.84 1.62
.circleincircle. 86.8 89.6 .circleincircle. I-1* 1.65 1.45
.largecircle. 57.5 66.4 X I-2* 1.46 1.25 X 58.6 66.8 X I-3* 1.52
1.31 X 56.8 64.5 X I-4* 1.75 1.54 .circleincircle. 53.2 60.5 X I-5*
1.56 1.33 .largecircle. 59.8 68.3 X I-6* 1.80 1.59 .largecircle.
56.8 65.6 .largecircle.
*: COMPARATIVE EXAMPLE
[0111] As will be seen from the data listed in Table 1, the ink
jet-recording sheet according to the present invention can ensure a
high density of printed images, can provide images having high
quality, shows only a slight color change and discoloration of
printed images even when exposed to ozone gas and is excellent in
the long-term shelf life.
EXAMPLE II-1
[0112] Preparation of Coating Liquid A for Forming Ink-Receiving
Layer
[0113] A coating liquid A for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fineseal X60 available from Tokuyama Co.,
Ltd.), 25 parts of silanol-modified polyvinyl alcohol (trade name:
R1130 available from Kuraray Co., Ltd.), 30 parts of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.), 100 parts of a 10%
aqueous solution of disodium 3,3'-thiodipropionate and small
amounts of an anti-foaming agent and a dispersant as well as water,
and which had a solid content of 15%.
[0114] Preparation of Ink Jet-Recording Sheet
[0115] The coating liquid A prepared above was applied onto
wood-free paper having a basis weight of 65 g/m.sup.2 in an amount
of 12 g/m.sup.2 as expressed in terms of the solid content using a
wire bar and then dried to form an ink-receiving layer. Thereafter,
the ink jet recording sheet thus formed was subjected to a
treatment with a super calender to thus form an ink jet-recording
sheet.
EXAMPLES II-2 TO II-8
[0116] The same procedures used in Example II-1 were repeated
except that the following compounds were substituted for the
disodium 3,3'-thiodipropionate used in Example II-1 to thus give
each corresponding ink jet-recording sheet.
EXAMPLE II-2
[0117] disodium 3,3'-dithiodipropionate
EXAMPLE II-3
[0118] disodium 2,2'-thiodiglycolate
EXAMPLE II-4
[0119] disodium 4,4'-thiodibutanoate
EXAMPLE II-5
[0120] disodium 6,6'-thiodicaproate
EXAMPLE II-6
[0121] diammonium 3,3-thiodipropionate
EXAMPLE II-7
[0122] calcium 3,3'-thiodipropionate
EXAMPLE II-8
[0123] magnesium 3,3'-thiodipropionate
EXAMPLE II-9
[0124] The same procedures used in Example II-1 were repeated
except that 50 parts of a 20% dispersion of 3,3'-thiodipropionic
acid prepared by the following method was substituted for 100 parts
of the 10% aqueous solution of disodium 3,3'-thiodipropionate to
thus form an ink jet-recording sheet.
[0125] Preparation of the Dispersion of 3,3'-Thiodipropionic
Acid
[0126] A dispersion was prepared by pulverizing a composition,
which comprises 100 parts of 3,3'-thiodipropionic acid, 5 parts of
sulfonate group-modified polyvinyl alcohol (trade name: Goselane
L-3266 available from The Nippon Synthetic Chemical Industry, Co.,
Ltd.), small amounts of a surfactant and an anti-foaming agent as
well as water and which had a solid content of 20% till the average
particle size was reduced to 0.5 .mu.m, using a sand grinder.
EXAMPLES II-10 AND II-11
[0127] The same procedures used in Example II-9 were repeated
except that the following compounds were substituted for the
3,3'-thiodipropionic acid used in Example II-9 to thus form each
corresponding ink jet-recording sheet.
EXAMPLE II-10
[0128] zinc 3,3'-thiodipropionate
EXAMPLE II-11
[0129] 3,3'-dithiodipropionic acid
EXAMPLE II-12
[0130] Preparation of Coating Liquid B for Forming Ink-Receiving
Layer
[0131] A coating liquid B for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fine Seal X60 available from Tokuyama Co.,
Ltd.), 25 parts of silanol-modified polyvinyl alcohol (trade name:
R1130 available from Kuraray Co., Ltd.), 30 parts of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.) and small amounts of an
anti-foaming agent and a dispersant as well as water, and which had
a solid content of 15%.
[0132] Preparation of Ink Jet-Recording Sheet
[0133] The coating liquid B prepared above was applied onto
wood-free paper having a basis weight of 65 g/m.sup.2 in an amount
of 12 g/m.sup.2 as expressed in terms of the solid content using a
wire bar and then dried to form an ink-receiving layer.
Subsequently, a 5% aqueous solution of di-sodium
3,3'-thiodipropionate was further applied onto the ink-receiving
layer using a wire bar in an amount of 11.0 g/m.sup.2 in terms of
solid and dried and then the layer was subjected to a super
calender treatment to thus form an ink jet-recording sheet.
EXAMPLE II-13
[0134] The same procedures used in Example II-12 were repeated
except that disodium 3,3'-dithiodipropionate was substituted for
the disodium 3,3'-thiodipropionate used in Example II-12 to form an
ink jet-recording sheet.
COMPARATIVE EXAMPLE II-1
[0135] The same procedures used in Example II-1 were repeated
except that disodium 3,3'-thiodipropionate was not used at all to
give an ink jet-recording sheet.
COMPARATIVE EXAMPLES II-2 and II-3
[0136] The same procedures used in Example II-9 were repeated
except that the following compounds were used in place of 100 parts
of the 3,3'-thiodipropionic acid to form each corresponding ink
jet-recording sheet.
COMPARATIVE EXAMPLE II-2
[0137] 100 parts of dilauryl 3,3'-thiodipropionate
COMPARATIVE EXAMPLE II-3
[0138] 100 parts of 2,6-di-tert-butyl-p-cresol
[0139] The ink jet recording sheets prepared in the foregoing
Examples and Comparative Examples were used in solid printing with
mixed black ink obtained by the color mixing of cyan, magenta and
yellow dyes and with cyan ink and also used in printing ISO-400
images ("Highly Precise and Fine Color Digital Standard Image Data:
ISO/JIS-SCID", p. 13, Kind of Image: Portrait, published by
Foundation: Nippon Kikaku Kyokai) using Epson Ink Jet Printer
PM-800C and then these sheets were evaluated in the same manner
used in Example I-1. The results thus obtained are listed in the
following Table 2. In this connection, a phthalocyanine dye is used
in PM-800C as a cyan dye.
2 TABLE 2 Resistance to Ozone Rate of Rate of Printed Quality
Remaining Remaining Ex. Density of Black Image Cyan Image No. Black
Cyan Image (%) (%) Image II-1 1.75 1.55 .circleincircle. 82.0 85.4
.circleincircle. II-2 1.73 1.51 .circleincircle. 84.3 87.2
.circleincircle. II-3 1.71 1.49 .largecircle. 77.5 79.8
.largecircle. II-4 1.68 1.46 .circleincircle. 73.6 77.3
.largecircle. II-5 1.65 1.45 .circleincircle. 72.5 76.4
.largecircle. II-6 1.75 1.51 .circleincircle. 83.2 86.5
.circleincircle. II-7 1.66 1.47 .largecircle. 81.2 83.5
.circleincircle. II-8 1.65 1.45 .largecircle. 82.2 84.7
.circleincircle. II-9 1.69 1.51 .largecircle. 82.5 86.2
.circleincircle. II-10 1.65 1.45 .largecircle. 81.6 84.6
.circleincircle. II-11 1.67 1.50 .largecircle. 83.6 86.2
.circleincircle. II-12 1.73 1.52 .largecircle. 82.6 85.7
.circleincircle. II-13 1.71 1.51 .largecircle. 84.7 86.5
.circleincircle. II-14 1.65 1.45 .largecircle. 57.5 66.4 X II-2*
1.46 1.25 X 58.6 66.8 X II-3* 1.52 1.31 X 56.8 64.5 X
*: COMPARATIVE EXAMPLE
[0140] As will be seen from the data listed in Table 2, the ink
jet-recording sheet according to the present invention can ensure a
high density of printed images, can provide images having high
quality, shows only a slight color change and discoloration of
printed images even when exposed to ozone gas and is excellent in
the long-term shelf life.
EXAMPLE III-1
[0141] Preparation of Dispersion of 3,3'-Dithiobis(2-Aminopropionic
Acid)
[0142] A dispersion was prepared by pulverizing a composition,
which comprised 100 parts of 3,3'-dithiobis(2-aminopropionic acid),
5 parts of sulfonate group-modified polyvinyl alcohol (trade name:
Goselane L-3266 available from The Nippon Synthetic Chemical
Industry, Co., Ltd.) and small amounts of a surfactant and an
anti-foaming agent as well as water, and which had a solid content
of 20% till the average particle size was reduced to 0.5 .mu.m,
using a sand grinder.
[0143] Preparation of Coating Liquid for Forming Ink-Receiving
Layer
[0144] A coating liquid for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fine Seal X60 available from Tokuyama Co.,
Ltd.), 250 parts of a 10% aqueous solution of silanol-modified
polyvinyl alcohol (trade name: R1130 available from Kuraray Co.,
Ltd.), 75 parts of a 40% aqueous solution of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.), 50 parts of a 20%
dispersion containing 3,3'-dithiobis(2-aminopropionic acid) and
small amounts of an anti-foaming agent and a dispersant as well as
water, and which had a solid content of 15%.
[0145] Preparation of Ink Jet-Recording Sheet
[0146] The coating liquid prepared above was applied onto wood-free
paper having a basis weight of 65 g/m.sup.2 in an amount of 12
g/m.sup.2 as expressed in terms of the solid content using a wire
bar and then dried to form an ink-receiving layer. Subsequently,
the ink-receiving layer was subjected to a super calender treatment
to thus form an ink jet-recording sheet.
EXAMPLES III-2 TO III-5
[0147] The same procedures used in Example III-1 were repeated
except that the following compounds were substituted for the
3,3'-dithiobis(2-aminopr- opionic acid) used in Example III-1 to
form each corresponding ink jet-recording sheet.
EXAMPLE III-2
[0148] 3,3'-dithiobis(2-aminopropionic acid)dihydrochloride
EXAMPLE III-3
[0149] 3,3'-thiobis(2-aminopropionic acid)
EXAMPLE III-4
[0150] dimethyl 3,3'-dithiobis(2-aminopropionate)
EXAMPLE III-5
[0151] 3,3'-dithiobis(2-N-acetylaminopropionic acid)
EXAMPLE III-6
[0152] Preparation of Coating Liquid for Forming Gloss-Developing
Layer
[0153] A coating liquid for forming a gloss-developing layer was
prepared, which comprised 100 parts of a composite of
styrene-2-ethylhexyl acrylate copolymer having a glass transition
temperature of 75.degree. C. and colloidal silica (the weight ratio
of the copolymer to the colloidal silica was set at 40:60), 5 parts
of a copolymer of alkyl vinyl ether and maleic acid derivative as a
thickening-dispersant and 3 parts of lecithin as a releasing agent
and which had a solid content of 30%.
[0154] Preparation of Ink Jet-Recording Sheet
[0155] An ink-receiving layer was formed on the surface of
wood-free paper having a basis weight of 65 g/m.sup.2 by applying
the coating liquid for forming an ink-receiving layer prepared in
Example III-1 in an amount of 12 g/m.sup.2 as expressed in terms of
the solid content using a wire bar and then dried. Immediately
after the coating liquid for forming a gloss-developing layer
prepared above was applied onto the ink-receiving layer, the layer
was pressed against a mirror-finished drum whose surface
temperature was set at 85.degree. C., followed by drying and
releasing the layer from the drum surface to thus give a glossy
type ink jet-recording sheet provided thereon with a glossy layer.
In this respect, the coated amount of the glossy layer was found to
be 8 g/m.sup.2 as expressed in terms of the solid content.
COMPARATIVE EXAMPLE III-1
[0156] The same procedures used in Example III-1 were repeated
except that the 3,3'-dithiobis(2-aminopropionic acid) was not used
at all to thus form an ink jet-recording sheet.
COMPARATIVE EXAMPLE III-2
[0157] The same procedures used in Example III-1 were repeated
except that dilauryl 3,3'-thiodipropionate was used in place of the
3,3'-dithiobis(2-aminopropionic acid) used in Example III-1 to thus
form an ink jet-recording sheet.
COMPARATIVE EXAMPLE III-3
[0158] The same procedures used in Example III-1 were repeated
except that 2,6-di-tert-butyl-p-cresol was used in place of the
3,3'-dithiobis(2-aminopropionic acid) used in Example III-1 to thus
form an ink jet-recording sheet.
COMPARATIVE EXAMPLE III-4
[0159] The same procedures used in Example III-6 were repeated
except that the 3,3'-dithiobis(2-aminopropionic acid) was not used
at all to thus form an ink jet-recording sheet.
[0160] The ink jet recording sheets prepared in the foregoing
Examples and Comparative Examples were used in solid printing with
mixed black ink obtained by the color mixing of cyan, magenta and
yellow dyes and with cyan ink and also used in printing ISO-400
images ("Highly Precise and Fine Color Digital Standard Image Data:
ISO/JIS-SCID", p. 13, Kind of Image: Portrait, published by
Foundation: Nippon Kikaku Kyokai) using Epson Ink Jet Printer
PM-800C and then these sheets were evaluated in the same manner
used in Example I-1. The results thus obtained are listed in the
following Table 3. In this connection, a phthalocyanine dye is used
in PM-800C as a cyan dye.
3 TABLE 3 Resistance to Ozone Rate of Rate of Printed Quality
Remaining Remaining Ex. Density of Black Image Cyan Image Image No.
Black Cyan Image (%) (%) Quality III-1 1.68 1.52 .largecircle. 82.6
86.7 .circleincircle. III-2 1.65 1.48 .largecircle. 82.4 86.4
.circleincircle. III-3 1.66 1.50 .largecircle. 73.4 76.4
.largecircle. III-4 1.67 1.52 .largecircle. 74.5 78.3 .largecircle.
III-5 1.65 1.49 .largecircle. 74.1 77.9 .largecircle. III-6 1.83
1.62 .circleincircle. 82.8 87.1 .circleincircle. III-1* 1.65 1.45
.largecircle. 57.5 66.4 X III-2* 1.46 1.25 X 58.6 66.8 X III-3*
1.52 1.31 X 56.8 64.5 X III-4* 1.77 1.56 .largecircle. 56.8 60.5
X
*: COMPARATIVE EXAMPLE
[0161] As will be seen from the data listed in Table 3, the ink
jet-recording sheet according to the present invention can ensure a
high density of printed images, can provide images having high
quality, shows only a slight color change and discoloration of
printed images even when exposed to ozone gas and is excellent in
the long-term shelf life.
EXAMPLE IV-1
[0162] Preparation of Dispersion of 1,4-Bis(Phenylthio)Butane
[0163] A dispersion was prepared by pulverizing a composition,
which comprised 100 parts of 1,4-bis(phenylthio)butane, 5 parts of
sulfonate group-modified polyvinyl alcohol (trade name: Goselane
L-3266 available from The Nippon Synthetic Chemical Industry, Co.,
Ltd.) and small amounts of a surfactant and an anti-foaming agent
as well as water, and which had a solid content of 20% till the
average particle size was reduced to 0.5 .mu.m, using a sand
grinder.
[0164] Preparation of Coating Liquid for Forming Ink-Receiving
Layer
[0165] A coating liquid for use in making an ink-receiving layer
was prepared, which comprised 100 parts of synthetic amorphous
silica (trade name: Fine Seal X60 available from Tokuyama Co.,
Ltd.), 250 parts of a 10% aqueous solution of silanol-modified
polyvinyl alcohol (trade name: R1130 available from Kuraray Co.,
Ltd.), 75 parts of a 40% aqueous solution of diallylamine
hydrochloride-acrylamide copolymer (trade name: Sumirez Resin 1001
available from Sumitomo Chemical Co., Ltd.), 50 parts of a 20%
dispersion containing 1,4-bis(phenylthio)butane and small amounts
of an anti-foaming agent and a dispersant as well as water, and
which had a solid content of 15%.
[0166] Preparation of Ink Jet-Recording Sheet
[0167] The coating liquid prepared above was applied onto wood-free
paper having a basis weight of 65 g/m.sup.2 in an amount of 12
g/m.sup.2 as expressed in terms of the solid content using a wire
bar and then dried to form an ink-receiving layer. Subsequently,
the ink jet recording sheet was subjected to a super calender
treatment to thus form an ink jet-recording sheet.
EXAMPLES IV-2 TO IV-5
[0168] The same procedures used in Example IV-1 were repeated
except that the following compounds were substituted for the
1,4-bis(phenylthio)butan- e used in Example IV-1 to form each
corresponding ink jet-recording sheet.
EXAMPLE IV-2
[0169] 1,6-bis(phenylthio)hexane
EXAMPLE IV-3
[0170] 1,4-bis(4-methylphenylthio)butane
EXAMPLE IV-4
[0171] 1,2-bis(phenylthio)ethane
EXAMPLE IV-5
[0172] Preparation of Coating Liquid for Forming Gloss-Developing
Layer
[0173] A coating liquid for forming a gloss-developing layer was
prepared, which comprised 100 parts of a composite of
styrene-2-ethylhexyl acrylate copolymer having a glass transition
temperature of 75.degree. C. and colloidal silica (the weight ratio
of the copolymer to the colloidal silica was set at 40:60), 5 parts
of a copolymer of alkyl vinyl ether and maleic acid derivative as a
thickening-dispersant and 3 parts of lecithin and which had a solid
content of 30%.
[0174] Preparation of Ink Jet-Recording Sheet
[0175] An ink-receiving layer was formed on the surface of
wood-free paper having a basis weight of 65 g/m.sup.2 by applying
the coating liquid for forming an ink-receiving layer prepared in
Example IV-1 in an amount of 12 g/m.sup.2 as expressed in terms of
the solid content using a wire bar and then dried. Immediately
after the coating liquid for forming a gloss-developing layer
prepared above was applied onto the ink-receiving layer, the layer
was pressed against a mirror-finished drum whose surface
temperature was set at 85.degree. C. to dry and the layer was
released from the drum surface to thus give a glossy type ink
jet-recording sheet provided thereon with a glossy layer. In this
respect, the coated amount of the glossy layer was found to be 8
g/m.sup.2 as expressed in terms of the solid content.
COMPARATIVE EXAMPLE IV-1
[0176] The same procedures used in Example IV-1 were repeated
except that the 1,4-bis(phenylthio)butane was not used at all to
thus form an ink jet-recording sheet.
COMPARATIVE EXAMPLE IV-2
[0177] The same procedures used in Example IV-1 were repeated
except that dilauryl 3,3'-thiodipropionate was used instead of the
1,4-bis(phenylthio)butane used in Example IV-1 to thus form an ink
jet-recording sheet.
COMPARATIVE EXAMPLE IV-3
[0178] The same procedures used in Example IV-1 were repeated
except that 2,6-di-tert-butyl-p-cresol was used instead of the
1,4-bis(phenylthio)butane used in Example IV-1 to thus form an ink
jet-recording sheet.
COMPARATIVE EXAMPLE IV-4
[0179] The same procedures used in Example IV-5 were repeated
except that the 1,4-bis(phenylthio)butane was not used at all to
thus form an ink jet-recording sheet.
[0180] The ink jet recording sheets prepared in the foregoing
Examples and Comparative Examples were used in solid printing with
mixed black ink obtained by the color mixing of cyan, magenta and
yellow dyes and with cyan ink and also used in printing ISO-400
images ("Highly Precise and Fine Color Digital Standard Image Data:
ISO/JIS-SCID", p. 13, Kind of Image: Portrait, published by
Foundation: Nippon Kikaku Kyokai) using Epson Ink Jet Printer
PM-800C and then these sheets were evaluated in the same manner
used in Example I-1. The results thus obtained are listed in the
following Table 4. In this connection, a phthalocyanine dye is used
in PM-800C as a cyan dye.
4 TABLE 4 Resistance to Ozone Rate of Rate of Printed Remaining
Remaining Quality Ex. Density Black Image Cyan Image of No. Black
Cyan (%) (%) Image IV-1 1.69 1.54 81.5 84.6 .circleincircle. IV-2
1.68 1.53 81.1 84.2 .circleincircle. IV-3 1.65 1.50 75.7 78.4
.largecircle. IV-4 1.63 1.51 73.5 76.7 .largecircle. IV-5 1.83 1.62
82.1 85.3 .circleincircle. IV-1* 1.65 1.47 57.5 66.5 X IV-2* 1.48
1.27 58.5 66.9 X IV-3* 1.53 1.32 56.8 64.5 X IV-4* 1.77 1.56 56.5
65.3 X
*: COMPARATIVE EXAMPLE
[0181] As will be seen from the data listed in Table 4, the ink
jet-recording sheet according to the present invention can ensure a
high density of printed images, shows only a slight color change
and discoloration of printed images even when exposed to ozone gas
and is excellent in the long-term shelf life.
* * * * *